Bis(tetramethylpiperidino)aluminum Halide Adducts tmp2AlX · Do and Tetrahaloaluminates of Tricoordinated Aluminum Cations [tmp2Al(Do)]AlX4

Krossing, Ingo; Nöth, Heinrich; Schwenk‐Kircher, Holger

doi:10.1002/(sici)1099-0682(199807)1998:7<927::aid-ejic927>3.0.co;2-i

Cited by 30 publications

(19 citation statements)

References 28 publications

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“…During this time, the color of the solution changed from dark yellow to green, which indicated the formation of 1a (87% spectroscopic yield, 1 H NMR). 1 49 The discrepancy between the data presented here and the literature can be attributed to an excess of BPh 3 present during the 1 H NMR experiment.…”

Section: ■ Experimental Sectioncontrasting

confidence: 81%

Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System

et al. 2021

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Bimetallic nitrogen (N2) splitting to form metal nitrides is an attractive method for N2 fixation. Although a growing number of pincer-supported systems can bind and split N2, the precise relationship between the ligand properties and N2 binding/splitting remains elusive. Here we report the first example of an N2-bridged rhenium(III) complex, [(trans-P2 tBuPyrr)ReCl2]2(μ-η1:η1-N2) (P2 tBuPyrr = [2,5-(CH2PtBu2)2C4H2N]−). In this case, N2 binding occurs at a higher oxidation level than that in other reported pincer analogues. Analysis of the electronic structure through computational studies shows that the weakly π-donor pincer ligand stabilizes an open-shell electronic configuration that leads to enhanced binding of N2 in the bridged complex. Utilizing SQUID magnetometry, we demonstrate a singlet ground state for this Re–N–N–Re complex, and we offer tentative explanations for antiferromagnetic coupling of the two local S = 1 sites. Reduction and subsequent heating of the rhenium(III)–dinitrogen complex leads to chloride loss and cleavage of the N–N bond with isolation of the terminal rhenium(V) nitride complex (P2 tBuPyrr)ReNCl.

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Section: ■ Experimental Sectioncontrasting

confidence: 81%

Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System

et al. 2021

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“…The 27 Al NMR of this product showed a signal at 70.3 ppm (Δ 1/2 = 2190 Hz) comparable to that of 7 (recorded in THF-d 8 with a very similar Δ 1/2 ). 41 The 1 H NMR of 8 showed AlMe at 0.32 ppm (-3.5 ppm for AlMe in 13 C NMR) and the 31 P{ 1 H} NMR showed a resonance at 35.40 ppm. 19 F NMR spectrum of this compound also showed an expected pattern and chemical shifts.…”

Section: Resultsmentioning

confidence: 99%

“…A broad signal in 27 Al NMR spectrum at 67.8 ppm in THF-d 8 supports monomeric nature of 7 (Δ 1/2 = 2180 Hz) perhaps due to THF coordination with Al thus increasing its coordination number and local symmetry. 29,41 It has been observed that the life time of the cationic species in THF is also high and can be anticipated due to the increase in coordination number around aluminium and partially compensating its Lewis acidic character. In order to confirm THF coordination at the cationic center of 7, a reaction (between 3 and B(C 6 F 5 ) 3 ) was carried out in THF as solvent.…”

Section: Resultsmentioning

confidence: 99%

A new bulky iminophosphonamide as an N,N′-chelating ligand: synthesis and structural characterization of heteroleptic group 13 element complexes

Prashanth

Singh

2014

Dalton Trans.

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A sterically demanding iminophosphonamine ligand [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]H (LH) and its lithium derivative [(2,6-iPr2C6H3N)P(Ph2)(NtBu)](Li·2THF) (1) were used to prepare complexes of group 13 elements. The reaction of LH with AlH3·NMe2Et and AlMe3 respectively, affords [LAlH2]2 (2) and LAlMe2 (3). The lithium derivative 1 when treated with the MCl3 compound of group 13 yields [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]MCl2 (M = B (4); Al (5); and Ga (6). Compound 3 on reaction with a Lewis acid B(C6F5)3 generates the cationic complex [{(2,6-iPr2C6H3N)P(Ph2)(NtBu)}AlMe](+) [MeB(C6F5)3](-) (7) that slowly undergoes rearrangement to yield [(2,6-iPr2C6H3N)P(Ph2)(NtBu)]AlMe(C6F5) (8) and MeB(C6F5)2. Compounds 1-8 were characterized using multinuclear NMR, EI-MS and IR techniques and the solid state structure of 1-6 and 8 was elucidated by single crystal X-ray diffraction analyses.

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“…Usually the bond lengths E-X increase as the coordination number increases. Typical examples are BCl 3 with (d(B-Cl) = 1.73Å [26] [27], or d(Al-Cl) in monomeric tmp 2 AlCl with 2.144Å versus the tetra-coordinated THF adduct, tmp 2 AlCl(THF), with 2.227Å [25,28]. The Al-Si bond in the tri-coordinated alane derivative tmp 2 AlSi(SiMe 3 ) 3 of 2.514(1)Å [28] is longer than the Al-Si bond lengths of 2.456(2)Å in the tetra-coordinate Al species [Cl 3 Al-Si(SiMe 3 ) 3 ] − .…”

Section: Discussionmentioning

confidence: 99%

Synthesis, Structure and Bonding in Triorganogermyl-alanes and Triphenylgermyl-aluminates

Habereder¹,

Nöth²,

Suter³

2009

Zeitschrift Für Naturforschung B

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Triphenylgermyl-lithium in diethyl ether/THF did not react with Al2Me6 to form [(Ph3Ge)AlMe3]- Li(THF)n. Addition of TMEDA to this solution yielded crystalline Ph3GeLi(THF)TMEDA. The reaction of Ph3GeLi in diethyl ether/hexane solution with H3Al-NMe3 in diethyl ether/THF generated [Ph3GeAlH3]Li(THF)4 while the reaction with Me2AlCl led to Ph3GeAlMe2(OEt2) and the trigermyl-aluminate [(Ph3Ge)3AlMe]Li. The analogous aluminate [(Ph3Ge)3AlH]Li(THF)3 was obtained by reacting LiGePh3 with AlH2Cl(OEt2) in the presence of THF. It was expected that the bulky bis(tetramethylpiperidino)chloroalane would react with Ph3GeLi to give the germyl-alane tmp2AlGePh3 which was observed when only diethyl ether was used as a solvent, but in an Et2O/toluene mixture only Ph8Ge3 could be isolated. Increasing the steric requirement of the germyllithium compound by using the bulky (tBu3Si)Me2Ge group instead of the Ph3Ge group led to a straightforward reaction generating the first structurally characterized germyl-alane (tBu3Si)Me2Ge- Al(tmp)2 with a planar tri-coordinated Al center. The X-ray structure determinations showed that the germyl-aluminates have shorter Ge-Al bonds than the germyl-alane inspite of the lower coordination number

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Bis(tetramethylpiperidino)aluminum Halide Adducts tmp2AlX · Do and Tetrahaloaluminates of Tricoordinated Aluminum Cations [tmp2Al(Do)]AlX4

Cited by 30 publications

References 28 publications

Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System

Electronic and Spin-State Effects on Dinitrogen Splitting to Nitrides in a Rhenium Pincer System

A new bulky iminophosphonamide as an N,N′-chelating ligand: synthesis and structural characterization of heteroleptic group 13 element complexes

Synthesis, Structure and Bonding in Triorganogermyl-alanes and Triphenylgermyl-aluminates

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